A general and benign iron-catalyzed alpha-alkylation reaction of ketones with primary alcohols has been developed. The key to success of the reaction is the use of a Knolker-type complex as catalyst (2 mol%) in the presence of Cs2CO3 as base (10 mol%) under hydrogen-borrowing conditions. Using 2-aminobenzyl alcohol as alkylation reagent allows for the "green" synthesis of quinoline derivatives.